Rare earths Solubilities

The lanthanides form many compounds with organic ligands. Some of these compounds ate water-soluble, others oil-soluble. Water-soluble compounds have been used extensively for rare-earth separation by ion exchange (qv), for example, complexes form with citric acid, ethylenediaminetetraacetic acid (EDTA), and hydroxyethylethylenediaminetriacetic acid (HEEDTA) (see Chelating agents). The complex formation is pH-dependent. Oil-soluble compounds ate used extensively in the industrial separation of rate earths by tiquid—tiquid extraction. The preferred extractants ate catboxyhc acids, otganophosphoms acids and esters, and tetraaLkylammonium salts. 

Fra.ctiona.1 Precipituition. A preliminary enrichment of certain lanthanides can be carried out by selective precipitation of the hydroxides or double salts. The lighter lanthanides (La, Ce, Pr, Nd, Sm) do not easily form soluble double sulfates, whereas those of the heavier lanthanides (Ho, Er, Tm, Yb, Lu) and yttrium are soluble. Generally, the use of this method has been confined to cmde separation of the rare-earth mixture into three groups light, medium, and heavy. 

Anhydrous ammonium oxalate is obtained when the monohydrate is dehydrated at 65°C. The monohydrate is a colorless crystal or white powder, and dissolves in water at 0°C up to 2.17 wt %, and 50°C up to 9.63 wt %. It is slightly soluble in alcohol and insoluble in ether. It is used for textiles, leather tanning, and precipitation of rare-earth elements. 

The solubility of rare-earth metals in /3-rh boron is unknown. Rare-earth-boron systems are cubic borides - with an composition (E = Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb). The occurrence of this phase excludes extensive solid solutions in... 

But first the synthesis had to come John was interested in reduced metal halides, particularly for the post-transition metals cadmium, galHum, and bismuth (his Ph.D. dissertation was on anhydrous aluminum halides and mixed halide intermediates, a good start for what was to come ). However, he was not yet actively interested in rare-earth metals and their remarkable solubility in their halides. But these elements lured him one floor below where Adrian Daane headed the metallurgy section of Spedding s empire. He knew how to produce rare-earth metals with high purity and in sufficient quantity and also how to handle tantalum containers. What if one gave it a tr/ and reduced some rare-earth metal halides (John insists that this term is used correctly) from their respective metals at high temperatures under appropriate conditions. 

In the case of molten salts, the functional electrolytes are generally oxides or halides. As examples of the use of oxides, mention may be made of the electrowinning processes for aluminum, tantalum, molybdenum, tungsten, and some of the rare earth metals. The appropriate oxides, dissolved in halide melts, act as the sources of the respective metals intended to be deposited cathodically. Halides are used as functional electrolytes for almost all other metals. In principle, all halides can be used, but in practice only fluorides and chlorides are used. Bromides and iodides are thermally unstable and are relatively expensive. Fluorides are ideally suited because of their stability and low volatility, their drawbacks pertain to the difficulty in obtaining them in forms free from oxygenated ions, and to their poor solubility in water. It is a truism that aqueous solubility makes the post-electrolysis separation of the electrodeposit from the electrolyte easy because the electrolyte can be leached away. The drawback associated with fluorides due to their poor solubility can, to a large extent, be overcome by using double fluorides instead of simple fluorides. Chlorides are widely used in electrodeposition because they are readily available in a pure form and... 

The rare earth oxides of lanthanum, samarium and gadolinium were converted into soluble nitrate salts by dissolving them in the minimum amount of concentrated nitric acid. Then two sets were prepared by adding 2.0 ml of aqueous solution of La(N03)3.6H20 [0.2 M] and 0.01 ml of (n-BuO)4Ti to 25 ml of aqueous solution of Cu(N03)2 [1.0 M]. Similarly, two sets were prepared with Co(N03)3. Same procedures were followed for Sm(N03)3 [0.2 M] and Gd(N03)3 [0.2 M], One set of all these solutions were sonicated under ultrasonic bath (Model - Meltronics, 20 kHz, 250 W) for half an hour. The solutions prepared in normal and sonicated conditions were kept in muffle furnace (Model - Deluxe Zenith) first at 100°C for 2 h and then the temperature of the furnace was raised up to 900°C and calcined for 2 h. The solid composites prepared were then cooled to room temperature and treated as catalyst for phenol degradation. 

The properties of elastomers are much improved by strain-induced crystallization, which occurs only in polymers with high stereoregularity. The polymerization of butadiene using completely soluble catalysts composed of a) rare earth carboxylates, b) Lewis acids and c) aluminum alkyls leads to polymers with up to 99 % cis-1,4 configuration. These polymers show more strain-induced crystallization than the commercial polybutadienes and consequently their processability is much improved. 

When we investigated catalysts based on rare earth carboxy-lates we found that most of them had extremely low solubility in hydrocarbon solvents, such as cyclohexane and n-hexane. 

We found that completely soluble compounds can be obtained in two ways. The first method, which is widely applicable, is to react a rare earth carboxylate with a small amount of an aluminum alkyl (11). Neodymium octoate can be converted into a product which is completely soluble in cyclohexane by reacting one mole of it with 1 to 5 moles of triethylaluminum. We also found that the rare earth salts of certain tertiary carboxylic acids are very readily soluble in non-polar solvents (12). In conjunction with a Lewis acid and aluminum alkyls, these compounds form highly active catalysts for the polymerization of butadiene. The neodymium Lewis acid aluminum alkyl molar ratio is within the range 1 (0.4-2.0) (10-40). 

There seem to be no direct calorimetric determinations of enthalpies of solution of rare-earth tribromides in nonaqueous solvents,3 and very few reports on the temperature variation of solubilities whence solution enthalpies might be roughly estimated. The most detailed set of data concerns cerium tribromide in pyridine (257). In this system there exists a series of solvates (cf. Section IH,C,2), but sufficient solubilities were determined for the estimation of enthalpies of solution of each solvate. These enthalpies are included in Fig. 3, which shows an extraordinary zig-zag variation of solubility with temperature. The actual values of enthalpies of solution cannot be accurate, but at least it is clear that they change sign and magnitude in an eccentric manner. 

The dependence of the solubility of LaCl3-7H20 on acid concentration at 25°C is indicated in Table XIX (205). The dependence at 50°C is the same. The dependence of solubilities of trichlorides of scandium (263), yttrium (264,265), and several rare-earth elements (265) on hydrochloric acid concentration has been established at 0°C. 

Solubilities of Rare-Earth Trichlorides in Ethylene Glycol and in Glycerol... 

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